CN104204060B - Polycarbonate compositions and the goods of formation thereof - Google Patents

Abstract

A kind of composition comprises at least one poly-(aliphatic ester)-Copolycarbonate, polysiloxane-polycarbonate copolymer and electromagnetic shielding agent (such as metallic fiber).When forming goods, said composition shows excellent impact characteristics and electromagnetic shielding characteristic.Another kind of composition comprises at least one poly-(aliphatic ester)-Copolycarbonate, polysiloxane-polycarbonate copolymer and carbon fiber.When forming goods, said composition has the impact characteristics of excellence.

Description

Polycarbonate compositions and the goods of formation thereof

Technical field

The disclosure relates generally to have HI high impact characteristic, good aesthetic value and useful in electromagnetic shielding is applied Polycarbonate compositions.There is disclosed herein the method for preparing and/or use said composition, and comprise this carbon of birdsing of the same feather flock together The goods of acid ester composite.

Background technology

Merlon (PC) is the synthesis engineered thermoplastic polymer derivative by bis-phenol and phosgene or their derivative.It Be linear carbonic acid polyester, and by dihydroxy compounds and carbonic diester or carbonylic halide, or ester exchange can be passed through And formed.Merlon is the useful classification polymer with many beneficial characteristics.

Consumer electronics market significantly increases in recent years.Nearest design object is very thin, have thinner wall and There is wider and bigger display board.Known compositions for this mobile device (such as mobile phone) can show fragility And/or cracking, ugly surface and/or poor mobility.

Due to various " quality critical " requirement of client, to combining electromagnetic shielding, there is favourable flowing, attractive in appearance and impact There is demand in the polycarbonate compositions of characteristic.

Summary of the invention

Disclosed herein is and show good impact, the attractive in appearance and various compositions of electromagnetic shielding characteristic.Said composition is usual Comprise at least one poly-(aliphatic ester)-Copolycarbonate, polysiloxane-polycarbonate copolymer and metallic fiber.This Based composition can be used for reducing and can be used, by electronic installation, the electromagnetic interference (EMI) caused.It is contemplated that these compositions Can be used for manufacturing and be used as such as the goods of case of electronic device.

It is disclosed that a kind of composition in some embodiments, comprises: first poly-(aliphatic ester)-polycarbonate-copolymerized Thing, it has from about 15,000Da to about 40, the weight average molecular weight of 000Da；Polysiloxane-polycarbonate copolymer；And electricity Magnetic screen agent；Wherein composition shows the notched Chalpy impact intensity of at least about 110J/m measured according to ASTM D256； And the glossiness of at least about 90 measured according to ASTM D2457 (at 20 °).

Said composition can comprise the electromagnetic shielding agent from about 5wt% to about 20wt%.This electromagnetic shielding agent can be metal Fiber, such as stainless steel fibre.Said composition can show the shield effectiveness of at least 40 decibels measured according to ASTM D4935.

This aliphatic ester can be derived by having the aliphatic dicarboxylic acid adding up to 8 to 12 carbon atoms.First poly-(fat Race's ester) the ester repetitive of-Copolycarbonate can derive by decanedioic acid.

Said composition can comprise first poly-(the aliphatic ester)-Copolycarbonate of the most about 85wt%.

In some embodiments, first poly-(aliphatic ester)-Copolycarbonate contains from about 2mol% to about The aliphatic ester unit of 13mol%.First poly-(aliphatic ester)-Copolycarbonate also can be containing about 87mol% to about The carbonate unit derivative from bisphenol-A of 98mol%.Aliphatic ester unit can be derived by decanedioic acid.

Said composition can further include the second poly-(aliphatic ester)-Copolycarbonate, wherein the second poly-(aliphatic Ester) weight average molecular weight of-Copolycarbonate is more than the Weight-average molecular of first poly-(aliphatic ester)-Copolycarbonate Amount.The weight ratio of first poly-(aliphatic ester)-Copolycarbonate and second poly-(aliphatic ester)-Copolycarbonate can From about 1:4 to about 5:2.

In embodiments, first poly-(aliphatic ester)-Copolycarbonate has from about 15,000Da to about 25, The weight average molecular weight of 000Da, and second poly-(aliphatic ester)-Copolycarbonate has from about 30,000Da to about 40, The weight average molecular weight of 000Da.Said composition can comprise first poly-(aliphatic ester)-poly-carbonic acid from about 10wt% to about 55wt% Ester copolymer.Said composition can comprise second poly-(aliphatic ester)-Copolycarbonate from about 5wt% to about 40wt%.

Said composition can comprise the polysiloxane-polycarbonate copolymer of the most about 70wt%.Polysiloxanes-poly-carbon The siloxane blocks chain length of acid ester copolymer is from about 30 to about 100, such as from about 35 to about 55.Polysiloxanes-poly-carbonic acid Ester copolymer can have the siloxane blocks content from about 15wt% to about 25wt%.Alternately, composition can have from about The siloxane blocks content of 0.5wt% to about 5wt%, comprises from about 0.9wt% to about 4.0wt%, or from about 2.0wt% to about 3.0wt%.Alternately, composition can have the total soft block contents less than 3.5wt%.In other embodiments, combination Thing comprises the siloxanes being derived from polysiloxane-polycarbonate copolymer of about 0.5wt% to about 6wt%.

In some embodiments, composition also can show the bending of at least about 2000Mpa measured according to ISO 178 Modulus.In other embodiments, composition also can show the breach of at least about 130J/m measured according to ASTM D 256 Cantilever beam impact strength.In other embodiments, composition shows the glossiness (at 20 °) of at least about 92.

In specific embodiment, composition shows the breach of at least about 140J/m measured according to ASTM D 256 Cantilever beam impact strength；The glossiness of at least about 92 measured according to ASTM D 2457 (at 20 °)；And according to ASTM The shield effectiveness of at least about 30 decibels of D4935 measurement.

In other embodiments, composition shows the gloss of measure at least about 98 according to ASTM D 2457 (at 60 °) Degree.

The most also being disclosed that to have and have at least 0.3mm and the goods of the wall less than 0.8mm thickness, these goods are by wrapping Making containing the most every composition: first poly-(aliphatic ester)-Copolycarbonate, it has from about 15, and 000Da is to about The weight average molecular weight of 40,000Da；Polysiloxane-polycarbonate copolymer；And electromagnetic shielding agent；Wherein composition shows Notched Chalpy impact intensity according at least about 110J/m that ASTM D256 measures；And according to ASTM D2457 (at 20 °) The glossiness of at least about 90 measured.

These goods can be mobile phone, MP3 player, computer, notebook, camera, video recorder, electronics Tablet PC, pager, hand telephone, video game machine, calculator, wireless automobile input unit, automobile component, filtration Device shell, luggage truck, office chair, kitchen appliance, electrical enclosure, electric connector, lighting, light emitting diode, electric component Or a part for telecommunications components.

Also disclose that a kind of composition in embodiments, comprise: first poly-(aliphatic ester)-polycarbonate-copolymerized Thing, it has from about 15,000Da to about 25, the weight average molecular weight of 000Da；Second poly-(aliphatic ester)-polycarbonate-copolymerized Thing, it has from about 30,000Da to about 40, the weight average molecular weight of 000Da；Polysiloxane-polycarbonate copolymer；And gold Belong to fiber；Wherein composition shows the notched Chalpy impact intensity of at least about 110J/m measured according to ASTM D256；With And the glossiness of at least about 90 measured according to ASTM D2457 (at 20 °).

The most more specifically it is disclosed that a kind of composition, comprises: first poly-(aliphatic ester)-poly-carbonic acid Ester copolymer, it has from about 15,000Da to about 40, the weight average molecular weight of 000Da；Polysiloxane-polycarbonate copolymer； And electromagnetic shielding agent；Wherein composition shows the notched izod punching of at least about 110J/m measured according to ASTM D256 Hit intensity；The glossiness of at least about 90 measured according to ASTM D2457 (at 20 °)；And measure extremely according to ASTM D4935 The shield effectiveness of few about 30 decibels.

It is disclosed that second group of polycarbonate compositions in other embodiments, comprises: first poly-(aliphatic ester)-poly- Carbonate copolymer, it has from about 15,000Da to about 40, the weight average molecular weight of 000Da；Polysiloxane-polycarbonate copolymerization Thing；And carbon fiber；Wherein composition shows at least 9.5kJ/m measured according to ISO 180 (23 DEG C, 3mm)²Breach hang Arm beam impact strength；And the multi-axial impact strength (MAI) of at least about 13J measured according to ASTM D3763 (23 °).

Composition can comprise first poly-(the aliphatic ester)-Copolycarbonate of the most about 85wt%.

Composition also can further include the second poly-(aliphatic ester)-Copolycarbonate, wherein the second poly-(aliphatic Ester) weight average molecular weight of-Copolycarbonate is more than the Weight-average molecular of first poly-(aliphatic ester)-Copolycarbonate Amount.

First poly-(aliphatic ester)-Copolycarbonate and the weight of second poly-(aliphatic ester)-Copolycarbonate Amount ratio is from about 1:4 to about 5:2.In some embodiments, first poly-(aliphatic ester)-Copolycarbonate has from about 15,000Da to about 25, the weight average molecular weight of 000Da, and second poly-(aliphatic ester)-Copolycarbonate has from about The weight average molecular weight of 30,000Da to about 40,000Da.Composition can comprise from the first of about 5wt% to about 50wt% the poly-(fat Race's ester)-Copolycarbonate.Composition can comprise second poly-(aliphatic ester)-poly-carbonic acid from about 5wt% to about 30wt% Ester copolymer.

Composition can comprise the polysiloxane-polycarbonate copolymer of the most about 70wt%.

In some embodiments, composition shows at least about 11kJ/m measured according to ISO 180 (23 DEG C, 3mm)² Notched Chalpy impact intensity；And the multi-axial impact strength of at least about 14J measured according to ASTM D3763 (23 °) (MAI)。

In certain embodiments, second group of composition shows and measures at least about according to ISO 180 (23 DEG C, 3mm) 9.5kJ/m²Notched Chalpy impact intensity；Multi-axial impact strength according at least about 13J that ASTM D3763 (23 °) measures (MAI)；The bending modulus of at least about 9000Mpa；And the gloss of at least about 10 measured according to ASTM D 2457 (at 20 °) Degree.

In other embodiments, second group of composition shows and measures at least about according to ISO 180 (23 DEG C, 3mm) 9.5kJ/m²Notched Chalpy impact intensity；Multi-axial impact strength according at least about 13J that ASTM D3763 (23 °) measures (MAI)；The bending modulus of at least about 10,000Mpa；And the light of at least about 15 measured according to ASTM D 2457 (at 20 °) Pool degree.

Also disclose that the goods being made up of second group of polycarbonate compositions.These goods can have and have at least 0.3mm And the wall less than 0.8mm thickness.

These and other non-restrictive characteristic is described in further detail below.

Detailed description of the invention

Geography can be easier to by the embodiment with reference to desired by following and the detailed description of embodiment wherein comprised Solve the disclosure.In following description and appended claims, refer to be defined as that there are the some of following meanings Term.

Singulative " a kind of ", " one " and " being somebody's turn to do " comprise plural reference object, unless the context clearly determines otherwise.

As used in the specification and in the claims, term " comprise " can comprise embodiment " by ... composition " and " substantially by ... composition ".

Numerical value in specification and claims of this application requirements, especially when them and polymer or polymer composition phase Guan Shi, its reflection is for comprising the mean value of the composition that thing is polymerized alone of different qualities.Additionally, unless there are contrary finger Showing, otherwise this numerical value is construed as comprising the numerical value identical when being decreased to the significant digits of equal number, and with described value Difference is less than determining the numerical value of the experimental error of the conventional measurement technology of type described in the application of this value.

All ranges disclosed herein comprises described end points and can be independently combinable (such as, " from about 2 grams to about 10 grams " Scope comprises end points, about 2 grams and about 10 grams, and all of median).The end points of these scopes disclosed herein and any numerical value It is not limited to exact extension or numerical value；They are the most coarse, in order to comprise the number being similar to these scopes and/or numerical value Value.

As used herein, approximating language can apply to modify any quantitative expression, this quantitative expression can change and It is not result in the change in its involved basic function.Therefore, by such as " about " and a term or multiple of " substantially " The value that term is modified is not limited to specified exact value in some cases.In at least some cases, approximating language can be right Should be in the instrument precision measuring this value.Modifier " about " is also considered as what disclosure was limited by the absolute value of two end points Scope.Such as, express " from about 2 to about 4 " and also disclose that scope " from 2 to 4 ".

Standardized denomination is used to describe compound.Such as, any position not being substituted by any indicated group is interpreted as Its chemical valence is filled by the key specified or hydrogen atom.The dash "-" between two letters or symbol does not takes for expression The tie point of Dai Ji.Such as, aldehyde groups-CHO is connected by the carbon of carbonyl group.

Term " aliphatic " refers to not to be ring-type and has the linear or branched row of atom of at least monovalence chemical valence Row.Aliphatic group is defined as comprising at least one carbon atom.The arrangement of atom may be embodied in the such as nitrogen of the hetero atom in main chain, Sulphur, silicon, selenium and oxygen, or can be made up of carbon and hydrogen uniquely.Aliphatic group can be substituted or unsubstituted.Example Property aliphatic group including but not limited to, methyl, ethyl, isopropyl, isobutyl group, hydroxymethyl (-CH₂OH), mercapto methyl (- CH₂SH), methoxyl group, methoxycarbonyl (CH₃OCO-), nitromethyla (-CH₂NO₂), and thiocarbonyl.

Term " alkyl " refers to the linear or branched arrangement of the atom being made up of uniquely carbon and hydrogen.The arrangement of atom is permissible Comprise singly-bound, double or triple bonds (commonly referred to alkane, alkene, or alkynes).Alkyl group can be substituted (i.e. one or many Individual hydrogen atom is replaced) or unsubstituted.Exemplary alkyl group is including but not limited to methyl, ethyl, and isopropyl.Should note Meaning, alkyl is aliphatic subset.

Term " aromatics " refers to have the arrangement of at least monovalence chemical valence and the atom that comprises at least one aromatic group. The arrangement of atom can comprise hetero atom such as nitrogen, sulphur, selenium, silicon and oxygen, or can be made up of carbon and hydrogen uniquely.Aromatic group Can be substituted or unsubstituted.Exemplary aromatic group including but not limited to, phenyl, pyridine radicals, furyl, thienyl, Naphthyl and xenyl.

Term " aryl " refers to the aromatic group being all made up of carbon atom and hydrogen atom.Number when aryl Yu carbon number Value scope combines when describing, and it is not construed as comprising substituted aromatic group.Such as, phrase " comprises from 6 to about 10 The aryl of carbon atom " should be interpreted that and only refer to phenyl (6 carbon atoms) or naphthyl (10 carbon atoms), and should not be explained For comprising methylphenyl group (7 carbon atoms).It should be noted that, aryl is the subset of aromatics.

Term " alicyclic " refers to the most non-aromatic ring-type atomic arrangement.Alicyclic group may be embodied in ring Hetero atom such as nitrogen, sulphur, selenium, silicon and oxygen, or can be made up of carbon and hydrogen uniquely.Alicyclic group can comprise one or Multiple noncyclic components.Such as, cyclohexyl methyl (C₆H₁₁CH₂-) it is cycloaliphatic functionality, it is (ring-type that it comprises cyclohexyl ring But it is not the arrangement of the atom of aromatics) and methylene group (noncyclic components).Alicyclic group can be to replace or unsubstituted 's.Exemplary cycloaliphatic group including but not limited to, cyclopropyl, cyclobutyl, 1, Isosorbide-5-Nitrae, 4-tetramethyl-ring butyl, piperidyl and 2, 2,6,6-tetramethyl-piperidyl.

Term " cycloalkyl " refers to ring-type but is not aromatics and the atomic arrangement being made up of carbon and hydrogen uniquely. Cycloalkyl can be substituted or unsubstituted.It should be noted that, cycloalkyl is the subset of cyclic aliphatic.

In above definition, term " substituted " refers to by such as alkyl, halogen ,-OH ,-CN ,-NO₂,-COOH etc. Another kind of functional group replace at least one hydrogen atom specified on group.

For the thin of mobile device but the design of larger part, it is provided that the material of electromagnetic shielding is expected to, because coming Interruption and fault may be caused in other electric device from the electromagnetic interference (EMI) of this device.EMI affects e.g. aviation Company usually requires that the reason that electronic installation cuts out during take-off and landing.High-impact is also desirable.Another Individual it is worth noting relevant with attractive in appearance；The molded parts with the filler projected from the surface is clumsy.

The disclosure relates generally to show good impact characteristics, balance the most attractive in appearance and have high electromagnetic shielding effect The polycarbonate compositions of energy.This polycarbonate compositions comprises (A) at least one poly-(aliphatic ester)-polycarbonate-copolymerized Thing, (B) polysiloxane-polycarbonate copolymer, and (C) electromagnetic shielding agent.The synergistic combination of these compositions provides excellent rushing Hit intensity, surface aesthetic and electromagnetic shielding.

As used herein, term " Merlon " and " carbonate polymer " refer to the repetitive structure with formula (1) The composition of carbonate unit:

Wherein R¹At least about the 60% of group total quantity is aromatic organic radicals, and its remaining part is aliphatic, fat Ring race or aromatic group.Ester units (-COO-) is not qualified as carbonate unit, and carbonate unit is not qualified as ester list Unit.In some embodiments, each R¹It is aromatic organic radicals, the such as group of formula (2):

-A¹-Y¹-A²- (2)

Wherein A¹And A²Each be monocyclic divalent aryl, and Y¹It is to have A¹And A²One or two atom separate Bridged group.In the exemplary embodiment, an atom is by A¹And A²Separately.The type group illustrative non-limiting Embodiment be-O-,-S-,-S (O)-,-S (O₂-C)-, (O)-, methylene, cyclohexyl-methylene, 2-[2.2.1]-dicyclo fork in heptan Base (bicycloheptylidene), ethidine, isopropylidene, new pentylidene base, cyclohexylidene base, ring 15 fork base (cyclopentadecylidene), ring ten y-bend base and adamantylidene base.Bridged group Y¹It can be hydrocarbyl group or saturated Hydrocarbyl group, such as subunit, cyclohexylidene base or isopropylidene.

Merlon can be by having formula HO-R¹The interfacial reaction of the dihydroxy compounds of-OH produces, wherein R¹As above State and defined.The dihydroxy compounds and the two of formula (3) of the dihydroxy compounds contained (A) being suitable in interfacial reaction Hydroxy compounds

HO-A¹-Y¹-A²-OH (3)

Wherein Y¹、A¹And A²As mentioned above.Also comprise is the bisphenol compound of formula (4):

Wherein R^aAnd R^bEach represent halogen atom or univalent hydrocarbyl group, such as C₁-C₃Alkyl group, and can identical or Different；P and q is the integer of 0 to 4 independently of one another；And X^aA kind of group in the group of expression (5):

Wherein R^cAnd R^dRepresent hydrogen atom or monovalent linear or cyclic hydrocarbon group, and R independently of one another^eIt it is divalent hydrocarbon Base group.

It is double (4-hydroxy phenyl) that the specific embodiment of the bisphenol compound type that can be represented by formula (3) comprises 1,1- Double (4-hydroxy phenyl) ethane of alkane, 1,1-, 2,2-double (4-hydroxy phenyl) propane (hereinafter " bis-phenol Α " or " BPA "), 2,2- Double (4-hydroxy phenyl) octane of double (4-hydroxy phenyl) butane, 2,2-, double (4-hydroxy phenyl) propane of 1,1-, double (the 4-hydroxyl of 1,1- Base phenyl) normal butane, double (4-hydroxyl-1-aminomethyl phenyl) propane of 2,2-and double (the 4-hydroxy-tert-butyl phenyl) propane of 1,1-.Also The combination containing at least one aforementioned dihydroxyl compound can be used.

The aromatic dihydroxy compound of other useful dihydroxy compounds contained (6):

The most each R^kIt is C independently₁-C₁₀Alkyl, and n is 0 to 4.Halogen is usually bromine.Can be represented by formula (6) COMPOUNDS EXAMPLE comprise resorcinol, substituted resorcinol compound, such as 5-base resorcinol, 5-phenyl isophthalic Diphenol, 5-cumyl resorcinol etc.；Catechol；Hydroquinones；Substituted hydroquinones, such as 2-methyl hydroquinone, uncle 2- Butylhydroquinone, 2-phenyl hydroquinones, 2-cumyl hydroquinones, 2,3,5,6-duroquinol etc.；Or comprise to The combination of few a kind of aforesaid compound.

Merlon also can branch.Point branching polycarbonate can be by adding branching agent system in polymerization process Standby.These branching agents comprise containing in the mixture of hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl and aforementioned functional groups The multifunctional organic compound of at least three kinds of functional groups.Specific embodiment comprises trimellitic acid, trimellitic anhydride, inclined benzene trigalloyl Chlorine, three-p-hydroxyphenylethane (THPE), isatin-diphenol, triphenol TC (1,3,5-tri-((p-hydroxybenzene) isopropyl) benzene), Triphenol PA (4 (4 (double (the p-hydroxybenzene)-ethyl of 1,1-) bis (alpha, alpha-dimethylbenzyl) base) phenol), 4-chloroformyl phthalic acid Acid anhydride, trimesic acid and benzophenone tetrabasic carboxylic acid.Branching agent can add with the level of about 0.05wt% to about 2.0wt%.

In a specific embodiment, the dihydroxy compounds for forming Merlon has a structure of formula (4a):

Wherein R₁To R₈It is each independently selected from hydrogen, nitro, cyano group, C₁-C₂₀Alkyl, C₄-C₂₀Cycloalkyl and C₆-C₂₀Aryl； And A is selected from key ,-O-,-S-,-SO₂-、C₁-C₁₂Alkyl, C₆-C₂₀Aromatic series and C₆-C₂₀Cyclic aliphatic.

In a specific embodiment, the dihydroxy compounds of formula (4a) is 2, double (4-hydroxy phenyl) propane of 2-(i.e. bis-phenol- A or BPA).Other illustrative of compounds of formula (I) comprises: double (4-hydroxyl-3-isopropyl phenyl) propane of 2,2-；Double (the 3-of 2,2- Tert-butyl-hydroxy phenyl) propane；Double (3-phenyl-4-hydroxy phenyl) propane of 2,2-；Double (4-hydroxy phenyl) hexamethylene of 1,1- Alkane；4,4' dihydroxy-1,1-biphenyl；4,4'-dihydroxy-3,3'-dimethyl-1,1-biphenyl；4,4'-dihydroxy-3,3'-two is pungent Base-1,1-biphenyl；4,4-dihydroxy diphenyl ether；4,4-dihydroxy diphenyl sulfide；(2-(4-hydroxy phenyl)-2-s third double with 1,3- Base) benzene.

The polycarbonate compositions of the disclosure contains at least two Copolycarbonate.First, polycarbonate compositions Comprise at least one poly-(aliphatic ester)-Copolycarbonate (A).This poly-(aliphatic ester)-Copolycarbonate is by carbon The combination composition of acid esters unit and aliphatic ester unit.Ester units can be extensively varied, such as with the mol ratio of carbonate unit From about 1:99 to about 99:1, or the most about 25:75 to 75:25, depend on the desirable characteristics of final composition.

Ester units can have a structure of formula (7):

Wherein m is from about 4 to about 18.In some embodiments, m is from 8 to 10.Ester units can be by C₆-C₂₀Fat Race's dicarboxylic acids (it comprises terminal carboxylic's ester group) or its reactive derivatives derive, and comprise C₈-C₁₂Aliphatic dicarboxylic acid.One In a little embodiments, terminal carboxylic's ester group derives, such as carboxylic acid halides (in particular from corresponding dicarboxylic acids or its reactive derivatives Acyl chlorides), ester etc..Exemplary dicarboxylic acids (corresponding acyl chlorides can derive from it) comprises C₆Dicarboxylic acids, such as adipic acid is (also referred to as Adipic acid)；C₁₀Dicarboxylic acids, such as decane diacid (also referred to as decanedioic acid)；And α, ω-C₁₂Dicarboxylic acids, such as dodecanedioic acid (has Time be referred to as DDDA).It will be appreciated that aliphatic dicarboxylic acid is not limited to these exemplary carbon chain lengths, and at C₆-C₂₀Scope Other interior chain length can use.

Poly-(the aliphatic ester)-Merlon with the ester units comprising straight chain methylene group and Merlon group is common The detailed description of the invention of polymers is shown in formula (8):

Wherein, m is about 3 to about 18；X and y represents averagely rubbing of aliphatic ester unit and carbonate unit in the copolymer That percentage.Molar average percentage x:y can be to about 1:99 from about 99:1, comprises from about 13:87 to about 2:98, or from about 9:91 to about 2:98 or from about 8:92 to about 13:87.Each R individually can derive from dihydroxy compounds.In concrete example In property embodiment, useful poly-(aliphatic ester)-Copolycarbonate comprises sebacate unit, and (formula (7), wherein m is 8) and there is the e.g., from about 2:98 bisphenol a carbonate unit to the average molar ratio of the x:y of about 8:92, such as 6:94).This poly- (aliphatic ester)-Copolycarbonate can be purchased (trade mark that LEXAN is SABIC IP B.V.) with LEXAN HFD copolymer.

In some embodiments, poly-(aliphatic ester) Copolycarbonate can have from about 15,000 to about 40,000 The weight average molecular weight of dalton (Da), comprises from about 20, and 000Da to about 38,000Da is (based on BPA polycarbonate standard by GPC Measure).This polycarbonate compositions can comprise from poly-(aliphatic ester) of about 20wt% to about 85wt%-polycarbonate-copolymerized Thing.

In some embodiments of the disclosure, polycarbonate compositions comprises two kinds of poly-(aliphatic ester)-Merlon Copolymer, i.e. first poly-(aliphatic ester)-Copolycarbonate (A1) and second poly-(aliphatic ester)-Copolycarbonate (A2).Two kinds of poly-(aliphatic ester)-Copolycarbonates can have identical or different ester units, and identical or different carbon Acid esters unit.

First poly-(aliphatic ester)-Copolycarbonate has (aliphatic ester)-Copolycarbonate more poly-than the second Lower weight average molecular weight.First poly-(aliphatic ester)-Copolycarbonate can have from about 15,000Da to about 25, The weight average molecular weight of 000Da, comprises from about 20, and (standard based on BPA polycarbonate is surveyed by GPC for 000Da to about 22,000Da Amount).With reference to formula (III), it is average that first poly-(aliphatic ester)-Copolycarbonate can have from about 7:93 to about 13:87 Molar percentage x:y.Second poly-(aliphatic ester)-Copolycarbonate can have about 30,000Da to about 40,000Da's Weight average molecular weight, comprises from about 35,000Da to about 38,000Da (based on BPA polycarbonate standard by gpc measurement).With reference to formula (III), second poly-(aliphatic ester)-Copolycarbonate can have the molar average percentage from about 4:96 to about 7:93 X:y.In embodiments, first poly-(aliphatic ester)-Copolycarbonate and second poly-(aliphatic ester)-Merlon are common The weight ratio of polymers can be from about 1:4 to about 5:2 (i.e. from about 0.25 to about 2.5).It should be noted that weight ratio as described herein is The ratio of the molecular weight of the ratio of the amount of two kinds of copolymers rather than two kinds of copolymers in the composition.Two kinds of poly-(aliphatic Ester) weight ratio between-Copolycarbonate will affect the mobility of final composition, ductility and surface aesthetic.Some Embodiment comprises high Mw copolymer more more than low Mw copolymer, i.e. second poly-(aliphatic ester)-Copolycarbonate with The ratio of first poly-(aliphatic ester)-Copolycarbonate is from 0:1 to about 1:1.Other embodiment comprises than high Mw altogether The more low Mw copolymer of polymers, i.e. second poly-(aliphatic ester)-Copolycarbonate and first poly-(aliphatic ester)-poly-carbon The ratio of acid ester copolymer is from 1:1 to about 5:2.Said composition can comprise from about 20wt% to the combination of about 85wt% One poly-(aliphatic ester)-Copolycarbonate (the lowest Mw copolymer) and second poly-(aliphatic ester)-Copolycarbonate (the highest Mw copolymer).Said composition can be containing from first poly-(the aliphatic ester)-Merlon of about 10wt% to about 55wt% Copolymer.Said composition can be containing from second poly-(the aliphatic ester)-Copolycarbonate of about 5wt% to about 40wt%.

Polycarbonate compositions also comprises polysiloxane-polycarbonate copolymer (B).It is embedding that this copolymer comprises Merlon Section and polydiorganosiloxanepolyurea block.Polycarbonate block in the copolymer comprises the repetitive structure list of formula described above (1) Unit, wherein R¹There is formula described above (2).These unit can be reacted by the dihydroxy compounds of formula as above (3) Derive.

The constitutional repeating unit (being sometimes herein referred to as " siloxanes ") of polydiorganosiloxanepolyurea block contained (9):

Wherein R occurs it being same or different every time, and is C_1-13Monovalent organic group.Such as, R can be C₁- C₁₃Alkyl group, C₁-C₁₃Alkoxy base, C₂-C₁₃Alkenyl group, C₂-C₁₃Alkenyloxy group group, C₃-C₆Group of naphthene base, C₃-C₆ Cycloalkoxy groups, C₆-C₁₀Aromatic yl group, C₆-C₁₀Aryloxy group, C₇-C₁₃Aromatic alkyl group, C₇-C₁₃Aralkyloxy groups, C₇-C₁₃Alkylaryl group or C₇-C₁₃Aryloxy alkyl group.The combination of aforementioned R group can use in same copolymer.Typically Ground, it is 2 to about 1000 that D can have mean value, specifically 2 to about 500, the most about 30 to about 100, or from about 35 to about 55, or alternately from 2 to about 20, or 5 to about 15.At D, there is lower value, such as, when less than about 40, it may be desirable to Use relatively large amount of polycarbonate-polysiloxane copolymer.On the contrary, when D has high value, when being greater than about 40, May need to use the polycarbonate-polysiloxane copolymer of relatively low quantities.D is properly termed as siloxane blocks chain length.

In some embodiments, polydiorganosiloxanepolyurea block is provided by the constitutional repeating unit of formula (10):

Wherein D is as defined above；Each R can be identical or different, and as defined above；And Ar can be identical or not With, and be substituted or unsubstituted C₆-C₃₀Arylene group, wherein key is directly connected to aromatic fractions.In formula (8) properly Ar group can be from C₆-C₃₀Dihydroxy arylene compound derives, the dihydroxy Asia virtue of such as above formula (3), (4) or (6) Based compound.The combination comprising at least one aforementioned dihydroxy arylene compound is used as.

This unit can derive from the corresponding dihydroxy compounds of following formula (11):

Wherein Ar and D is described above.The compound of this formula can pass through dihydroxy arlydene chemical combination under condition of phase transition The reaction of thing and such as α, ω-biacetyl epoxide polydiorganosiloxanepolyurea and obtain.

The constitutional repeating unit of polydiorganosiloxanepolyurea block contained (12) in another embodiment:

Wherein R and D is as defined above.R in formula (12)²It is the C of divalence₂-C₈Aliphatic group.Every in formula (12) Individual M can be identical or different, and can be cyano group, nitro, C₁-C₈Alkylthio group, C₁-C₈Alkyl, C₁-C₈Alkoxyl, C₂-C₈Alkene Base, C₂-C₈Alkenyloxy group, C₃-C₈Cycloalkyl, C₃-C₈Cycloalkyloxy, C₆-C₁₀Aryl, C₆-C₁₀Aryloxy group, C₇-C₁₂Aralkyl, C₇- C₁₂Aralkoxy, C₇-C₁₂Alkaryl or C₇-C₁₂Aryloxy alkyl, the most each n is 0,1,2,3 or 4 independently.

In some embodiments, M is alkyl, such as methyl, ethyl or propyl group, alkoxy base, such as methoxyl group, second Epoxide or propoxyl group, or aromatic yl group, such as phenyl or tolyl；R²It is dimethylene, trimethylene or tetramethylene base Group；And R is C_1-8Alkyl, haloalkyl such as trifluoro propyl, cyanoalkyl, or aryl such as phenyl or tolyl.Separately In one embodiment, R is methyl, or methyl and the mixture of phenyl.In another embodiment, M is methoxyl group, n It is 1, R²It it is divalence C₁-C₃Aliphatic group, and R is methyl.

These unit can derive from corresponding dihydroxy polydiorganosiloxanecan (13):

Wherein R, D, M, R²Described above with n.

This polysiloxanediol can manufacture by realizing platinum catalysis addition between the silicone hydride of (14),

Wherein R and D is as defined above, and aliphatic unsaturation monohydric phenol.Suitably aliphatic unsaturation monohydric phenol Comprise, such as eugenol, 2-chavicol, 4-chavicol, 4-pi-allyl-2-methylphenol, 4-pi-allyl-2-benzene Base phenol, 4-pi-allyl-2-tert-butoxy phenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-pi-allyl- 4,6-xylenol, 2-pi-allyl-6-methoxyl group-4-methylphenol and 2-pi-allyl-4,6-xylenol.Comprise at least The mixture of a kind of aforementioned substances can also use.

In a particular embodiment, when the Ar of formula (8) is from resorcinol derived, polydiorganosiloxanepolyurea repetitive Derive from the polysiloxanes bis-phenol of formula (15):

Or when Ar is to derive from bisphenol-A, derive from the polysiloxanes bis-phenol of formula (16):

Wherein D is as defined above.

In other specific embodiment, polysiloxane unit is to derive from the polysiloxanes bis-phenol of formula (17):

Wherein D is as described in formula (7).

In other detailed description of the invention, polysiloxane unit is spread out from the polysiloxanes bis-phenol of formula (18) or formula (19) Raw:

Wherein D is as described in formula (7).

Siloxane blocks can be formed to the polysiloxane-polycarbonate copolymer of about 25wt% by more than zero, comprises from about 4wt% to about 25wt%, from about 4wt% to about 10wt%, or from about 15wt% to about 25wt%.Polycarbonate block can be by about The block copolymer composition of 75wt% to less than about 100wt%, comprises from about 75wt% to about 85wt%.Especially it is considered that gather Siloxane-polycarbonate copolymer is diblock copolymer.This polysiloxane-polycarbonate copolymer can have from about 28, The weight average molecular weight of 000Da to about 32,000Da.This polycarbonate compositions can comprise the poly-silicon from about 5wt% to about 70wt% Oxygen alkane-Copolycarbonate, comprises from about 5wt% to about 20wt%, or from about 15wt% to about 65wt%.It is being embodied as In mode, composition comprises the siloxanes being derived from polysiloxane-polycarbonate copolymer of about 0.5wt% to about 6wt%.Poly-silicon The amount (by weight) of oxygen alkane-Copolycarbonate there may come a time when less than poly-(aliphatic ester)-Copolycarbonate (A) Amount, generally reduces at least about 10wt% or at least 20wt% of said composition.Alternately, polysiloxane-polycarbonate copolymerization The amount of thing can limit by contributing to total siloxane blocks content of overall polycarbonate compositions.At embodiment In, gross weight based on composition, composition can have the siloxane blocks content from about 0.5wt% to about 5wt%, comprise from About 0.9wt% is to about 4.0wt%, or from about 2.0wt% to about 3.0wt%.Exemplary commercially available polysiloxane-polycarbonate Copolymer by SABIC IP B.V. with markEXL sells.

If necessary, poly-(aliphatic ester)-Copolycarbonate (A) can comprise other monomer.Similarly, If necessary, polysiloxane-polycarbonate copolymer (B) can comprise other monomer.These Copolycarbonates Can be manufactured by method as known in the art such as interfacial polymerization and melt phase polycondensation.Although for interfacial polymerization Reaction condition is it may happen that change, but illustrative methods is usually directed to dihydric phenol reactant is dissolved or dispersed in caustic soda Or in the caustic potash aqueous solution, gained mixture is added to suitably and in the immiscible solvent medium of water, and suitably urging In the presence of agent such as triethylamine or phase transfer catalyst, under the conditions of the pH controlled, e.g., from about 8 to about 10, by reactant and carbon Acid esters precursor thereof.Usually, in melt polymerization process, Merlon can beMixer, twin-screw squeeze Go out in machine etc. in the presence of ester exchange catalyst, in the molten state by by dihydroxy reactants with diaryl carbonate such as Diphenyl carbonate reacts jointly to be prepared thus forms homogeneous dispersion.Volatile monohydric phenol is by distilling from frit reaction thing Remove, and polymer is separated into melted residue.

Polycarbonate compositions also comprises electromagnetic shielding agent (C).Usually, electromagnetic shielding agent is metallic fiber.At electromagnetism The metallic fiber used in screener can be the metallic fiber of any conduction.Suitably metal comprises iron, copper, aluminium, nickel, titanium, And the alloy of aforementioned metal.The combination of aforementioned metal it is also contemplated that.In some embodiments, electromagnetic shielding agent is stainless Steel fibre.Stainless steel fibre includes comprising iron and chromium, nickel, carbon, manganese, molybdenum, the mixture etc. that comprises at least one aforementioned substances Those of alloy.Suitably stainless steel composition is specified also dependent on conventional grade such as Stainless steel 316, stainless steel 347 etc.. All above-mentioned materials are commercially available.Such as, stainless steel fibre can be purchased from Bekaert with trade name BEKI-SHIELD.

In some embodiments, the length of metallic fiber can be from about 1 millimeter to about 30 millimeter after molding.? In other embodiment, the length of metallic fiber can be at least about 3 millimeters after molding.In other embodiments, gold The length belonging to fiber can be at least 5 millimeters after molding.In other embodiments, the length of metallic fiber is at molding Before can be at least about 10 millimeters.In other embodiments, the length of metallic fiber can be at maximum up to about after molding 20 millimeters.In other embodiments, the length of metallic fiber can be at maximum up to about 15 millimeters after molding.At molding After, the length of metallic fiber can be less than above-mentioned regulation.Such as, in some embodiments, metallic fiber is long after molding Degree can be about 30 microns to about 3 millimeters.

The diameter of metallic fiber can be from about 3 microns to about 20 microns after molding and afterwards.Other embodiment party In formula, the diameter of metallic fiber can be at least about 8 microns.In other embodiments, the diameter of metallic fiber can be most Reach about 15 microns.In other embodiments, the diameter of metallic fiber can be at maximum up to about 12 microns.Other embodiment party In formula, the diameter of metallic fiber can be at maximum up to about 10 microns.

In an alternative embodiment, electromagnetic shielding agent comprises metal-coated fiber.Suitable core for metal-coated fiber Material can comprise vitreous mineral, such as glass, aluminosilicate, magnesium silicate, calcium-silicate etc.；With DIC material such as stone Ink, carbon dust, carbon fiber, mica etc..Any metal that can strengthen thermoplastic resin shield effectiveness can serve as metal coating fibre The metal coating of dimension.Suitably metal comprises silver, gold, copper, aluminium, nickel, platinum, comprises the alloy of at least one aforementioned metal, comprises The combination etc. of at least one aforementioned metal.In some embodiments, metal-coated fiber is silver coating vitreous mineral fiber. Metal-coated fiber can have and for size identical described in metallic fiber.

Gross weight based on metal-coated fiber, the tenor in metal-coated fiber can be to about from about 1wt% 30wt%.In an alternative embodiment, metal-coated fiber can use the metal of at least about 10wt%.At other embodiment In, metal-coated fiber can use the metal of the most about 20wt%.In other embodiments, metal-coated fiber can To use the metal of at maximum up to about 15wt%.

In some embodiments, before and after composition extrusion and/or molding, metal-coated fiber length is permissible It is from about 25 microns to 600 microns.In other embodiments, before and after composition extrusion and/or molding, metal is coated with Cover fibre length and can be at least 50 microns.In other embodiments, gold before and after composition extrusion and/or molding Belonging to coated fiber length can be at least about 150 microns.In other embodiments, before composition extrusion and/or molding Metal-coated fiber length can be at maximum up to 500 microns afterwards.In other embodiments, composition extrusion and/or Before and after molding, metal-coated fiber length can be at maximum up to about 300 microns.In other embodiments, at composition Before and after extrusion and/or molding, metal-coated fiber length can be at maximum up to about 300 microns.

In some embodiments, the diameter of metal-coated fiber can be from about 1 micron to about 10 micron.Real at other Executing in mode, the diameter of metal-coated fiber can be at least about 3 microns.In other embodiments, metal-coated fiber Diameter can be at least 5 microns.In other embodiments, the diameter of metal-coated fiber can be at maximum up to about 8 microns.? In other embodiment, the diameter of metal-coated fiber can be at maximum up to about 6 microns.

Gross weight based on composition, electromagnetic shielding agent can be present in combination from about 5wt% to the amount of about 20%wt% In thing.In other embodiments, gross weight based on composition, electromagnetic shielding agent can the amount of at least about 3wt% be present in In composition.In other embodiments, gross weight based on composition, electromagnetic shielding agent can be at maximum up to about 20wt%'s Amount is present in composition.In another embodiment, gross weight based on composition, electromagnetic shielding agent can about 5wt% Amount to about 15%wt% is present in composition.

In some embodiments, electromagnetic shielding agent is substantially free of metal dust and sheet metal.Term is " the most not Contain " it is defined herein as gross weight based on composition, the amount limiting powder or thin slice is less than about 0.1wt%.Real at other Executing in mode, powder or thin slice exist with less than about 0.01wt%.In other embodiments, powder or thin slice be not with any Amount is deliberately added in electromagnetic shielding agent.

In other embodiments, gross weight based on described composition, composition contains and comprises from 0.5wt% to about The metal dust of 10wt% and/or the electromagnetic shielding agent of sheet metal.Suitably metal dust and thin slice can comprise iron, silver, aluminium, Nickel, copper, comprise the alloy of at least one aforementioned metal, comprises the mixture etc. of at least one aforementioned metal.Fiber, powder and thin Sheet can draw ratios based on them and be distinguished from each other.Fiber can be defined as the equal draw ratio of number with greater than about 3, Qi Zhongchang Footpath is than the ratio being defined as length and equivalent diameter.On the other hand, the number that thin slice can be defined as less than 0.25 is equal Draw ratio, and powder can be defined as the equal draw ratio of number with 0.25 to about 3.

In some embodiments, polycarbonate compositions also comprises impact modifier (D).Impact modifier can comprise bullet The graft copolymer that gonosome is modified, this elastomer-modified graft copolymer comprises (i) elastomer (i.e. rubber-like) polymer base Matter, it has the glass transition temperature (Tg) of less than about 10 DEG C, more especially less than about-10 DEG C, or the most about-40 DEG C To-80 DEG C, and rigid polymer upper strata material (superstrate) that (ii) is grafted on elastic polymer matrix.As known , elastomer-modified graft copolymer can be then poly-in the presence of elastomer by first providing elastomer polymer The composition monomer closing rigidity phase is prepared to obtain graft copolymer.Graft can be connected to elastomer as grafted branch or shell Core.Shell can merely physically encapsulate core body, or shell can partially or substantially completely be grafted on core body.

Suitable material as elastomer phase comprises, such as conjugated diene rubber；Conjugated diene is with less than about 50wt%'s The copolymer of copolymerisable monomer；Olefinic rubber, such as ethylene propylene copolymer (EPR) or Ethylene-Propylene-Diene monomer rubber (EPDM)；Ethylene-vinyl acetate rubber；Silicon rubber；Elastic C_1-8Alkyl (methyl) acrylate；C_1-8Alkyl (methyl) propylene Acid esters and butadiene and/or cinnamic elastocopolymer；Or comprise the combination of at least one foregoing elastomers.As made herein , term " (methyl) acrylate monomer " is referred to as ground and is referred to acrylate monomer and methacrylate monomers.

Such concrete impact modifier is that MBS (MBS) is impact-resistant modified Agent, wherein butadiene matrix uses above-mentioned sulfonate, sulfate or phosphate as surfactant to prepare.Other example The elastomer-modified graft copolymer of property comprises acrylonitrile-butadiene-styrene (ABS) (ABS), acrylonitrile-styrene-acrylic acid fourth Ester (ASA), methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS), and acrylonitrile-vinyl-propylenediene-benzene Ethene (AES).

In some embodiments, described impact modifier is the graft polymers with high rubber content, i.e. with grafting Polymer weight meter, greater than or equal to about 50wt%, is optionally greater than or equal to about 60wt%.Rubber preferably with less than or etc. In about 95wt%, the amount of the graft polymers being alternatively less than or being equal to about 90wt% exists.

The mixture of grafted monomers can also use, to provide graft copolymer.Suitably mixture embodiment comprises list Vinyl-arene and acrylic monomer.The graft copolymer embodiment being suitable for using is including but not limited to, acrylic nitrile-butadiene two Alkene-styrene (ABS) and methacrylonitrile-butadiene-styrene (MBS) resin.Suitable high rubber acrylonitrile-butadiene- Styrene resin, can from SABIC (former GE) withGrade 131,336,338,360 and 415 obtain.

In some embodiments, polycarbonate compositions comprises the poly-(aliphatic from about 20wt% to about 85wt% Ester)-Copolycarbonate (A)；From the polysiloxane-polycarbonate copolymer (B) of about 5wt% to about 70wt%；With from about The electromagnetic shielding agent (C) of 5wt% to about 20wt%.When it is present, impact modifier (D) can be from about 2wt% to about 8wt%'s Amount exists.These values are gross weights based on composition.It should be pointed out that, at least one poly-(aliphatic ester)-Merlon Copolymer (A) can be the blend of two or more Copolycarbonates with different weight average molecular weight, Yi Jisuo The about 20wt% enumerated refers to the total amount of the most this kind of Copolycarbonate (A) to about 85wt%.

In other embodiments, polycarbonate compositions comprises and has from about 15,000Da to about 25, the Mw's of 000Da From poly-(the aliphatic ester)-Copolycarbonate (A1) of about 10wt% to about 55wt%；Have from about 30,000Da to about 40, Poly-(the aliphatic ester)-Copolycarbonate (A2) from about 5wt% to about 40wt% of the Mw of 000Da；From about 5wt% to about The polysiloxane-polycarbonate copolymer (B) of 70wt%；And from the electromagnetic shielding agent (C) of about 5wt% to about 20wt%.

Polycarbonate compositions has good impact strength, high gloss and the combination of effective electromagnetic shielding.They At least there is the breach overarm arm impact strength of at least about 110J/m measured according to ASTM D 256；And according to ASTM D2457 (at 20 °) measure at least about 90 glossiness.

When in the thickness measure of 23 DEG C, 5 pounds and 3.2 millimeters, polycarbonate compositions can show according to ASTM D 256 Breach overarm arm impact strength (NII) of at least about 110J/m measured.In some embodiments, the breach cantilever of composition Beam impact strength is at least about 130J/m, comprises at least about 150J/m.Notched Chalpy impact intensity can reach a maximum of about of 200J/ m。

Polycarbonate compositions can show and at least about 90 (comprise at least according to what ASTM D2457 (at 20 °) measured About 92) glossiness.Glossiness can reach the largest of about 97.In some embodiments, when 20 DEG C of measurements, glossiness has Above-mentioned value, and when having the glossiness of at least about 98 when measuring for 60 DEG C.In this respect, the instruction of higher gloss value is more smooth Surface, and 20 ° of angles are more more sensitive for surface roughness than 60 ° of measurements.

When measuring according to ISO 178, polycarbonate compositions can have the bending modulus of at least 2000 MPas (Mpa), bag Containing at least 2300Mpa or at least 2400Mpa.Bending modulus has reached the maximum of 2600Mpa.

In some embodiments, polycarbonate compositions can have according to the electromagnetic shielding effect for measuring planar materials The U.S. of fruit tests the shield effectiveness of at least about 30 decibels measured with materials association (ASTM) standard method of test (D4935). In other embodiments, composition has the shield effectiveness of at least about 30 decibels.In another embodiment, composition tool There is the shield effectiveness of at least 50 decibels.

Polycarbonate compositions can have any combination of these characteristics (NII, glossiness, bending modulus, shield effectiveness), Any combination with the values listed of these characteristics.It should be noted that, some characteristics (such as NII) use by polycarbonate composition The goods that thing is made measure；But, such characteristic is referred to as belonging to this polycarbonate compositions, in order to reference.

In some embodiments, composition show according to ASTM D 256 measure at least about 110J/m breach hang Arm beam impact strength；The glossiness of at least about 90 measured according to ASTM D 2457 (at 20 °)；And according to ASTM D4935 The shield effectiveness of at least about 30 decibels measured.

In some embodiments, composition show according to ASTM D 256 measure at least about 110J/m breach hang Arm beam impact strength；The glossiness of at least about 90 measured according to ASTM D 2457 (at 20 °)；With measure according to ISO 178 The bending modulus of at least about 2000 MPas.

In some embodiments, composition show according to ASTM D 256 measure at least about 130J/m breach hang Arm beam impact strength；Glossiness with at least about 90 measured according to ASTM D 2457 (at 20 °).

In some embodiments, composition show according to ASTM D 256 measure at least about 110J/m breach hang Arm beam impact strength；Glossiness with at least about 92 measured according to ASTM D 2457 (at 20 °).

In some embodiments, composition show according to ASTM D 256 measure at least about 140J/m breach hang Arm beam impact strength；The glossiness of at least about 92 measured according to ASTM D 2457 (at 20 °)；And according to ASTM D4935 The shield effectiveness of at least about 30 decibels measured.

In some embodiments, composition show according to ASTM D 256 measure at least about 110J/m breach hang Arm beam impact strength；The glossiness of at least about 90 measured according to ASTM D 2457 (at 20 °)；And according to ASTM D 2457 (at 26 °) measure at least about 98 glossiness.

In some embodiments, composition show according to ASTM D 256 measure at least about 110J/m breach hang Arm beam impact strength；The glossiness of at least about 90 measured according to ASTM D 2457 (at 20 °).

Other additive being routinely incorporated in this type polycarbonate compositions is used as, and condition is this additive It is selected for the most significantly, adversely affecting the desirable characteristics of Merlon.The combination of additive can be used.These additives can To mix during forming the composition mixing of composition at reasonable time.In embodiments, one or more add Add agent selected from following at least one: UV stabilization additives, thermal stabilization additive, releasing agent, colouring agent and Gamma-stable agent.

Exemplary anti-oxidant additives comprises such as organic phosphite, such as three (nonyl phenyl) phosphite ester, Three (2,4-di-tert-butyl-phenyl) phosphite ester (such as " IRGAFOS 168 " or " I-168 "), double (2,4-di-tert-butyl-phenyls) Pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite etc.；Alkylation monophenols or polyphenols；Polyphenol and alkadienes Alkylation reaction product, such as four [methylene (3,5-di-t-butyl-4-hydroxy hydrocinnamate)] methane etc.；Paracresol Or the butylation product of bicyclopentadiene；Alkylated hydroquinone；Hydroxylation thiodiphenyl ethers；Alkylidenebisphenols；Benzylation Compound；β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and unitary or the ester of polyalcohol；β-(5-tertiary butyl-4-hydroxy-3-first Base phenyl) propionic acid and unitary or the ester of polyalcohol；Alkylthio or the ester of thioaryl compounds, such as distearyl sulphur generation third Acid esters, dilauryl thiopropionate, double tridecyl thiodipropionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyl Phenyl) propionic ester, pentaerythrite base-four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester etc.；β-(3,5-di-t-butyl- 4-hydroxyphenyl) acid amides etc. of propionic acid；Or comprise the combination of at least one aforementioned antioxidant.Antioxidant generally with The amount of total polycarbonate compositions of 0.0001wt% to about 1wt% uses.

Exemplary thermostable agent addition agent comprises such as organic phosphite, such as triphenyl phosphite, three (2,6-diformazans Base phenyl) phosphite ester, three (the single-and di-nonyl phenyl of mixing) phosphite ester etc.；Phosphonate ester, such as dimethyl benzene phosphonic acids Ester etc., phosphate, such as trimethyl phosphate etc., or comprise the combination of at least one aforementioned heat stabilizer.Heat stabilizer generally with The amount of total polycarbonate compositions of 0.0001wt% to about 1wt% uses.

It is used as light stabilizer and/or ultraviolet light (UV) absorbing additives.Exemplary light stabilizer additive comprises example Such as benzotriazole, such as 2-(2-hydroxy-5-methyl base phenyl) BTA, 2-(2-hydroxyl-5-t-octyl phenyl) benzo three Azoles and UV-531 etc., or comprise the combination of at least one aforementioned light stabilizer.Light stabilizer is usual Use with the amount of total polycarbonate compositions of 0.0001wt% to about 1wt%.

Exemplary UV absorbing additives comprises such as, dihydroxy benaophenonel；Hydroxybenzotriazole；Hydroxy benzo triazine；Cyanogen Base acrylate；Butoxanilide；Benzoxazinone；2-(2H-BTA-2-base)-4-(1,1,3,3-tetramethyl butyl)- PhenolUV-5312-[4,6- Double (2,4-3,5-dimethylphenyl)-1,3,5-triazine-2-base]-5 (octyloxy)-phenol2,2'- (1,4-phenylene) double (4H-3,1-benzoxazin-4-one)1,3-pair [(2-cyano group- 3,3-diphenylacryloyl) epoxide] double [[(2-cyano group-3,3-diphenylacryloyl) epoxide] methyl] propane of-2,2-2,2'-(1,4-phenylene) double (4H-3,1-benzoxazin-4-one)；1,3-pair [(2-cyano group- 3,3-diphenylacryloyl) epoxide] double [[(2-cyano group-3,3-diphenylacryloyl) epoxide] methyl] propane of-2,2-；Receive Meter level inorganic material, such as titanium oxide, cerium oxide and zinc oxide, all particle diameters all having less than or equal to about 100 nanometers；Deng Deng, or comprise the combination of at least one aforementioned UV absorbent.UV absorbent is generally with the total poly-carbon of 0.0001wt% to about 1wt% The amount of acid ester composite uses.

It is used as plasticizer, lubricant and/or releasing agent.Exist the most overlapping between the material of these types, its Comprise such as phthalic acid ester, such as dioctyl-4,5-epoxy hexahydrophthalic acid ester；Three (octoxycarbonylethyl) are different Cyanurate；Tristearin；Two-or multifunctional aromatic phosphate acid esters, such as resorcinol tetraphenyldiphosphate (RDP), to benzene Double (diphenyl) phosphates of diphenol and double (diphenyl) phosphates of bisphenol-A；Poly-alpha-olefin；Epoxidised soybean oil；Silicone Class, comprises silicone oil；Esters, such as fatty acid ester, such as alkyl stearyl, such as methyl stearate, stearyl stearate, Pentaerythritol tetrastearate (PET) etc.；Methyl stearate and comprise polyethylene glycol polymer, polypropylene glycol polymers, poly-(second Glycol co-propylene glycol) combination of hydrophilic and hydrophobic non ionic surfactants of copolymer, or comprise such as at suitable solvent In methyl stearate and the combination of at least one foregoing glycols polymer of polyethylene glycol propylene glycol copolymers；Wax, such as Beeswax, lignite wax, paraffin etc..This material generally with 0.001wt% to about 1wt%, be especially 0.01wt% to 0.75wt%, The more particularly amount of total polycarbonate compositions of 0.1wt% to 0.5wt% uses.

In addition to titanium dioxide (D), other colouring agent such as pigment and/or dye additive can also exist, with Just offset and may be present in any color in polycarbonate resin, and the color needed for offer is to client.Useful pigment can wrap Containing such as inorganic pigment, such as metal oxide such as zinc oxide, the iron oxide etc. of metal oxide and mixing；Sulfide such as zinc sulphide Deng；Aluminate；Sulfo group sodium metasilicate (sodium sulfo-silicates), sulfate, chromate etc.；Carbon black；Zinc ferrite；Ultramarine Blue；Organic pigment such as AZOpigments, disazo pigment, quinacridone, naphthalene tetracarboxylic acid, yellow scholar's ketone, isoindolinone, tetrachloro Isoindolinone, anthraquinone, anthrone, dioxazines, phthalocyanine and azo lake；Paratonere 101, pigment red 122, pigment red 149, pigment Red 177, pigment red179, paratonere 202, pigment violet 29, pigment blue 15, pigment blue 60, pigment Green 7, pigment yellow 119, pigment yellow 147 and pigment yellow 150, and pigment brown 24；Or comprise the combination of at least one aforesaid pigments.Pigment is generally with about 0.01wt% extremely The amount of total polycarbonate compositions of about 10wt% uses.

Exemplary dyes is typically organic material, and comprises such as coumarine dye such as cumarin 460 (blue), cumarin 6 (green), Nile red etc.；Lanthanide Complexes；Hydrocarbon and substituted hydrocarbon dyestuff；Polycyclic aromatic hydrocarbon dyestuff；Scintillation dyes, such as oxazole or evil two Thiiazole dye；Aryl-or heteroaryl-substituted poly-(C2-8) alkene dyestuff；Carbonyl cyanine dye；Indanthrone dyes；Phthalocyanine dye；Dislike Piperazine dyestuff；Carbon styryl (carbostyryl) dyestuff；Naphthalene tetracarboxylic acid dyestuff；Porphyrin dye；Double (styryl) biphenyl contaminates Material；Acridine dye；Anthraquinone dye；Cyanine dye；Methine dyes；Arylmethane dyes；Azo dyes；Indigoid dye, sulphur are for indigo Class dyestuff, bisazo dye；Nitro dye；Quinoneimine dye；Aminoketone dye；Tetrazolium dye；Thiazole dye；Dye Material；Ketone dyes；Two-benzoxazolyl thiophene (BBOT)；Triarylmethane dye；Ton dyestuff；Thioxanthene dye；Naphthalene two formyl Imide dye；Lactone colouring matters；Fluorogen, such as anti-Stokes shift dyes, it absorbs near-infrared wavelength and also launches visible wavelength, Etc.；Luminescent dye, such as 7-amino-4-methylcoumarin；3-(2 '-benzothiazolyl)-7-diethyl amino coumarin；2- (4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles；2,5-pair-(4-xenyl)-oxazole；2,2 '-dimethyl- P-quaterphenyl；2,2-dimethyl-p-terphenyl；", 3,5,3 " 5 " "-tetra-tert-p-quinquephenyl；2,5-diphenyl furans； 2,5-diphenyloxazole；4,4 '-diphenyl stilbene；4-dicyano methylene-2-methyl-6-is (to dimethylamino Styryl)-4H-pyrans；1,1 '-diethyl-2,2 '-carbocyanine iodide；3,3 '-diethyl-4,4 ', 5,5 '-dibenzo Sulphur generation three carbocyanine iodide；7-dimethylamino-1-methyl-4-methoxyl group-8-azepine quinolone-2；7-dimethylamino- 4-methyl quinolone-2；2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethyl-benzothiazole perchloric acid Salt；3-diethylamino-7-diethyl imino group phenoxazine azoles perchlorate；2-(1-naphthyl)-5-oxazolyl phenyl；2,2 '-p- Phenylene-two (5-oxazolyl phenyl)；Rhodamine 700；Rhodamine 800；Pyrene；Bend (chrysene)；Rubrene；Coronene etc., or Comprise the combination of at least one abovementioned dyes.Dyestuff is generally with total polycarbonate compositions of about 0.01wt% to about 10wt% Amount uses.

Stable radiation agent can also exist, particularly γ stable radiation agent.Exemplary γ-stable radiation agent comprises alkylidene Polyalcohol, as ethylene glycol, propane diols, 1,3-PD, 1,2-butanediol, BDO, meso 2,3-butanediol, 1,2- Pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexylene glycol etc.；Cycloalkylidene polyalcohol, such as 1,2-ring pentanediol, 1,2- Cyclohexanediol etc.；Branched alkylene groups polyalcohol, such as Pinacol (pinacol) etc., and alkoxyl replaces Ring-type or acyclic alkanes.Undersaturated alkenols is also useful, and embodiment comprises 4-methyl-4-amylene-2-alcohol, 3- Methyl pentene-3-alcohol, 2-methyl-4-amylene-2-alcohol, 2,4-dimethyl-4-amylene-2-alcohol (2,4-dimethyl-4-pene- 2-ol) and 9-decen-1-ol, and there is the tertiary alcohol of the substituted tertiary carbon of at least one hydroxyl, such as 2-methyl-2,4-penta 2 Alcohol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-benzene-2-butanol etc., and the ring-type tertiary alcohol is such as 1-hydroxyl-1-methyl-cyclohexyl alkane.The hydroxyl having being connected in the saturated carbon of undersaturated carbon in aromatic ring can also be used Base some methylol aromatic compounds substituted.The substituted saturated carbon of this hydroxyl can be methylol (-CH₂Or it can OH), To be more complicated alkyl such as-CR⁴HOH or-CR⁴The member of OH, wherein R⁴It it is complicated or simple hydrocarbon.Concrete hydroxymethyl Aromatic compounds comprises benzohydrol, 1,3-benzene dimethanol, benzylalcohol, 4-benzyloxybenzyl alcohol and benzyl benzylalcohol.2-methyl-2,4- Pentanediol, polyethylene glycol and polypropylene glycol are usually used in γ stable radiation.γ stable radiation compound is generally with about 0.1wt% extremely The amount of the overall polycarbonate compositions of about 10wt% uses.

Polycarbonate compositions can be molded into pellet.Said composition can pass through known method, as injection, Overmolded (overmolding), extrusion, rotational molding, blowing and thermoforming mould, foamed or be extruded into various structure or article. Especially, the goods benefiting from EMI shielding are considered, such as electronic equipment, electronic housings or electronic building brick.Non-limiting enforcement Example comprises computer case, components of mobile phone, hand-hold electronic device, as MP3 player, electronic plane computer, pager, Camera shell, video recorder, video game machine, calculator, wireless automobile input unit, automobile component, filter housings, luggage Car and office chair, kitchen appliance, electric housing etc., such as intelligence instrument housing etc.；Electric connector, and lighting, ornaments, Household electrical appliance, light emitting diode (LED) and the assembly of tabula rasa, extruded films and sheet-like article；Electric component, such as relay；With Telecommunications components, such as the parts of base station terminal.The disclosure it is contemplated within extra on described goods manufacture operation, such as but It is not limited to, molding, in-mold decoration, baking in paint oven, lamination and/or thermoforming.Polycarbonate compositions is for manufacturing Have and have at least 0.3mm and particularly useful less than the goods of 0.8mm thickness parts.

The disclosure separately relates to show second group of polycarbonate compositions of the impact characteristics of improvement.These poly-carbonic acid Ester composition comprises (A) at least one poly-(aliphatic ester)-Copolycarbonate, (B) polysiloxane-polycarbonate copolymerization Thing, and (E) carbon fiber.

The structure of at least one poly-(aliphatic ester)-Copolycarbonate (A) has been described above.This polysiloxanes- The structure of Copolycarbonate (B) is the most as already identified above.Description before those is also applied for this Merlon of second group Composition.

In the polycarbonate compositions of second group, poly-(aliphatic ester)-Copolycarbonate (A) can have from about 15,000Da to about 40, the weight average molecular weight of 000Da, comprise from about 20,000Da to about 38,000Da is (based on BPA polycarbonate Standard is by gpc measurement).Second group of polycarbonate compositions can comprise from poly-(aliphatic ester) of about 10wt% to about 85wt%- Copolycarbonate.

Sometimes, second group of polycarbonate compositions comprises two kinds of poly-(aliphatic ester)-Copolycarbonates, and i.e. first gathers (aliphatic ester)-Copolycarbonate (A1) and second poly-(aliphatic ester)-Copolycarbonate (A2).Both copolymerization Thing (A1) and the molecular weight of (A2) and weight ratio are as previously mentioned.Second group of composition can comprise from about 10wt% to about 85wt%'s First poly-(aliphatic ester)-Copolycarbonate (copolymer of the lowest Mw) of combination and second poly-(aliphatic ester)-poly-carbon Acid ester copolymer (copolymer of the highest Mw).Composition can containing from first poly-(aliphatic ester) of about 5wt% to about 50wt%- Copolycarbonate.Said composition can be containing common from second poly-(the aliphatic ester)-Merlon of about 5wt% to about 30wt% Polymers.

Second group of polycarbonate compositions can comprise the polysiloxane-polycarbonate copolymerization from about 5wt% to about 70wt% Thing, comprises from about 5wt% to about 20wt%, or from about 15wt% to about 65wt%.The amount of polysiloxane-polycarbonate copolymer (by weight) sometimes can be usually less than the amount of poly-(aliphatic ester)-Copolycarbonate (A), generally reduce group At least about 10wt% or at least 20wt% of compound.Alternately, the amount of polysiloxane-polycarbonate copolymer can be by having The total siloxane blocks content helping overall polycarbonate compositions limits.In embodiments, gross weight based on composition Amount, second group of polycarbonate compositions can have the siloxane blocks content from about 0.5wt% to about 5wt%, comprise from about 0.9wt% is to about 4.0wt%, or from about 2.0wt% to about 3.0wt%.

Carbon fiber (E) is present in second group of polycarbonate compositions.Carbon fiber is similar with previously described metallic fiber, But mainly by carbon or all it is made up of carbon.Carbon fiber can have the length from about 1 millimeter to about 30 millimeter after molding, comprises The most at least about 3 millimeters, at least about 5 millimeters, at least about 10 millimeters, at maximum up to about 20 millimeters, or the most about 15 millimeters.After molding, the length of metallic fiber can be less than defined above.Such as, in some embodiments, at molding Carbon fiber length afterwards can comprise from about 30 microns to about 3 millimeters from about 25 microns to about 600 microns, or at least about 50 Micron, or at least about 150 microns, at maximum up to about 500 microns, at maximum up to about 400 microns, or at maximum up to about 300 microns. After molding and afterwards the diameter of carbon fiber can be from about 4 microns to about 20 microns.In other embodiments, carbon fiber Diameter can be from about 1 micron to about 10 micron, at least about 8 microns, at maximum up to about 15 microns, at maximum up to about 12 microns, or At maximum up to about 10 microns.Carbon fiber can the amount more than zero to about 30wt% exist, and comprises from about 5wt% to about 30wt%.

In some embodiments, second group of polycarbonate compositions comprises the poly-(fat from about 10wt% to about 85wt% Fat race ester)-Copolycarbonate (A)；From the polysiloxane-polycarbonate copolymer (B) of about 5wt% to about 70wt%；With From the carbon fiber (E) of about 5wt% to about 30wt%.When it is present, impact modifier (D) can be from about 2wt% to about 8wt%'s Amount exists.These values are gross weights based on composition.It should be pointed out that, at least one poly-(aliphatic ester)-Merlon Copolymer (A) can be the blend of two or more Copolycarbonates with different weight average molecular weight, and institute The about 10wt% enumerated refers to the total amount of the most this kind of Copolycarbonate (A) to about 85wt%.

In other embodiment, second group of polycarbonate compositions comprises from about 5wt% having to about 50wt% From about 15,000Da to poly-(the aliphatic ester)-Copolycarbonate (A1) of the Mw of about 25,000Da；From about 5wt% to about 30wt% has poly-(the aliphatic ester)-Copolycarbonate (A2) from about 30,000Da to the Mw of about 40,000Da；From The polysiloxane-polycarbonate copolymer (B) of about 5wt% to about 70wt%；With from about 5wt% to the carbon fiber of about 20wt% (E)。

Second group of polycarbonate compositions has the impact strength of improvement.They at least have according to ISO 180 (23 DEG C, 3 Millimeter) at least about 9.5kJ/m that measures²Breach overarm arm impact strength (NII)；Measure with according to ASTM D3763 (23 DEG C) The multi-axial impact strength (MAI) of at least about 13J.

In more specifically embodiment, the second group of polycarbonate composition measured according to ISO 180 (23 DEG C, 3 millimeters) The NII of thing at least about 11kJ/m²。

In other detailed description of the invention, the second group of polycarbonate compositions measured according to ISO 6603 (23 DEG C) MAI at least about 14J, or at least about 15J, or at least about 16J.

Second group of polycarbonate compositions can show the gloss of measure at least 7 according to ASTM D2457 (at 20 °) Degree, comprises at least about 10 and at least about 15.Glossiness can reach the peak of about 30.

Second group of polycarbonate compositions can have the bending modulus of at least 850MPa when measuring according to ISO 178, bag Containing at least about 9000MPa or at least about 10,000MPa.Bending modulus has reached the maximum of about 15,000MPa.

Similarly, second group of polycarbonate compositions can have these characteristics (NII, MAI, glossiness, bending modulus) Any combination, and any combination of the values listed of these characteristics.It should be noted that, some characteristics (such as NII) use by gathering The goods that carbonate composition is made measure；But, such characteristic is referred to as belonging to this polycarbonate compositions, in order to In reference.

In some embodiments, second group of composition show according to ISO 180 (23 DEG C, 3mm) measure to Few about 9.5kJ/m²Notched Chalpy impact intensity；Multiaxis punching according at least about 13J that ASTM D3763 (23 DEG C) measures Hit intensity (MAI)；The bending modulus of at least about 9,000Mpa；And at least about 10 measured according to ASTM D 2457 (at 20 °) Glossiness.

In other detailed description of the invention, second group of composition show according to ISO 180 (23 DEG C, 3mm) measure to Few about 9.5kJ/m²Notched Chalpy impact intensity；Multiaxis punching according at least about 13J that ASTM D3763 (23 DEG C) measures Hit intensity (MAI)；The bending modulus of at least about 10,000Mpa；And measure at least about according to ASTM D 2457 (at 20 °) The glossiness of 15.

The interpolation of filler would generally reduce the impact strength of polycarbonate compositions, especially NII and MAI.Therefore, not phase The combination hoping height flowing Merlon, polysiloxane-polycarbonate copolymer and carbon fiber will show higher impact strength.

The following examples are provided to the polycarbonate compositions of the disclosure, goods and method are described.This embodiment is only It is merely illustrative, it is not intended that the disclosure is limited to material, condition or the technological parameter illustrated wherein.

Embodiment

The Name and Description of the composition used in the examples below listed by table 1.

Table 1

Condition listed by use table 2 and table 3 mixes and molds composition described below.Except stainless steel fibre Outside, polycarbonate powder is pre-mixed with other composition.Premixing powder uses double screw extruder extrusion.During extrusion stainless Steel fibre feeds at independent feeder downstream.Mixing condition is listed in table 2.Condition of moulding is listed in table 3.

Table 2

Set	Unit	Value
			Barrel size	mm	1500
Die head	mm	430
			Region 1 temperature	℃	50
Region 2 temperature	℃	100
			Barrel temperature	℃	280
Die head temperature	℃	280
			Screw speed	rpm	400
Output	Kg/hr	40
			Moment of torsion	%	47
Vacuum 1	MPa	0.8

Table 3

Step	Unit	Value
			Pre-drying-time	Hour	3
Predrying temperature	℃	120
			Hopper temperature	℃	50
Region 1 temperature	℃	275

Region 2 temperature	℃	290
			Region 3 temperature	℃	300
Nozzle temperature	℃	300
			Molding temperature	℃	100
Screw speed	rpm	80
			Back pressure	kgf/cm2	70
Injection speed	mm/s	20
			Keep pressure	kgf/cm2	1800
Shift pressure	kgf/cm2	2000

Notched Chalpy impact intensity (NII) uses ASTM D256,5 pounds, 23 DEG C and 3.2mm thickness measure.NII also makes Measure by ISO 180,23 DEG C, 3 mm of thickness.Non-notch cantilever beam test (UNI) uses ISO 180,23 DEG C, 3 millimeters thick Degree is measured.

Bending modulus and bending strength according to ISO 178 at indoor temperature measurement.

Polyaxial impact (MAI) is measured with 4.4m/s according to ISO 6603.

Chord modulus was measured with 50mm/ minute in room temperature according to ISO 527.Stress and strain value exists according to ISO 527 Room temperature was measured with 50mm/ minute.

Glossiness measures at 20 DEG C and 60 DEG C according to ASTM D2457.

Shield effectiveness uses Eddy current method to measure.This result is unit report with decibel (dB).

Heat deflection temperature (HDT) measures under 1.8Mpa according to ISO 75.

Embodiment E1-E8

List in composition table below 4A and 4B of four comparing embodiments C1-C4 and eight embodiments E1-E8.By In rounding up, summation may not be added to 100wt%.

Table 4A

Composition	Unit	C1	C2	C3	C4	E1	E2	E3	E4
										PAEBPALow	Wt%				52.55	43.55	31.55	22.55	13.55
PAEBPAHigh	Wt%				35.03	29.03	21.03	15.03	9.03
										PCLow	Wt%		52.55	46.55
PCHigh	Wt%		35.03	31.03
										PC-Si-1	Wt%		0	10
PC-Si-2	Wt%	88				15	35	50	65
										ADR 4368	Wt%		0.08	0.08	0.08	0.08	0.08	0.08	0.08
Phosphite	Wt%		0.08	0.08	0.08	0.08	0.08	0.08	0.08
										PTFE	Wt%		0.25	0.25	0.25	0.25	0.25	0.25	0.25
SSF	Wt%	10	10	10	10	10	10	10	10
										Black concentrate	Wt%	2	2	2	2	2	2	2	2
Si%		5.28	0	2	0	0.9	2.1	3	3.9
										PAEBPALow/PAEBPAHigh					1.5	1.5	1.5	1.5	1.5
Bending modulus.	MPa	2450	2565	2412	2642	2495	2472	2415	2387

Bending strength	MPa	89	93	86	93	90	89	88	88
										NII,ISO	kJ/m2	11	9	16	9	13	15	14	13
UNI,ISO	kJ/m2	51	118	98	111	115	112	91	88
										NII,ASTM	J/m	124	119	170	87	110	139	145	132
MAI,23℃	J/m	9	25	29	20	27	24	15	11
										MAI-20℃	J/m	10	5	8	2	4	4	10	11
Chord modulus	MPa	2506	2705	2575	2586	2501	2496	2454	2411
										Yield stress	MPa	56	59	56	59	57	56	55	54
Fracture strength	MPa	48	47	45	43.96	43	44	45	46
										Yield strain	%	4	5	5	4.57	4	4	4	4
Yield strain	%	5	10	8	4.57	4	4	4	4
										Glossiness, 20 °		85.3	85.6	89.6	84.4	93.5	93.4	92.2	93.8
Glossiness, 60 °		98.7	99.1	99.6	98.6	98.8	99.2	98.9	96.4
										Shield effectiveness	dB	48	44	43	42	41	42	43	42

Table 4B

Composition	Unit	C1	C2	C3	C4	E5	E6	E7	E8
										PAEBPALow	Wt%				52.55	49.55	46.55	43.55	40.55
PAEBPAHigh	Wt%				35.03	33.03	31.03	29.03	27.03
										PCLow	Wt%		52.55	46.55
PCHigh	Wt%		35.03	31.03
										PC-Si-1	Wt%		0	10		5	10	15	20
PC-Si-2	Wt%	88
										ADR 4368	Wt%		0.08	0.08	0.08	0.08	0.08	0.08	0.08
Phosphite	Wt%		0.08	0.08	0.08	0.08	0.08	0.08	0.08
										PTFE	Wt%		0.25	0.25	0.25	0.25	0.25	0.25	0.25
SSF	Wt%	10	10	10	10	10	10	10	10
										Black concentrate	Wt%	2	2	2	2	2	2	2	2
Si%		5.28	0	2	0	1	2	3	4
										PAEBPALow/PAEBPAHigh					1.5	1.5	1.5	1.5	1.5
Bending modulus	MPa	2450	2565	2412	2642	2419	2380	2347	2391
										Bending strength	MPa	89	93	86	93	86	84	82	81
NII,ISO	kJ/m2	11	9	16	9	16	17	18	18
										UNI,ISO	kJ/m2	51	118	98	111	133	131	104	108
NII,ASTM	J/m	124	119	170	87	145	164	173	180
										MAI,23℃	J/m	9	25	29	20	34	30	34	27
MAI-20℃	J/m	10	5	8	2	3	6	9	9
										Chord modulus	MPa	2506	2705	2575	2586	2483	2437	2460	2413
Yield stress	MPa	56	59	56	59	56	55	53	52
										Fracture strength	MPa	48	47	45	43.96	43	43	42	41
Yield strain	%	4	5	5	4.57	4	4	4	4
										Yield strain	%	5	10	8	4.57	4	4	4	4
Glossiness, 20 °		85.3	85.6	89.6	84.4	95.7	93.4	92.1	91.6
										Glossiness, 60 °		98.7	99.1	99.6	98.6	99.7	100	99.2	98.4
Shield effectiveness	dB	48	44	43	42	41	42	42	43

C1 comprises the PC-Si without Merlon, and C2 comprises the bisphenol A homo thing without PC-Si, and C3 comprises There is the bisphenol A homo thing of a small amount of PC-Si.Relatively, there is the least difference in C1 and C2 on NII and glossiness.Close In C3, NII and glossiness exist little improvement.

In C4, poly-(aliphatic ester)-Copolycarbonate (PAE-BPA) is used to replace bisphenol A homo thing and not There is PC-Si.NII is approximately the 73% of C2, and glossiness also reduces.

In E1-E4, PC-Si-2 adds in different amounts.Along with the amount of PC-Si-2 increases, NII also increases.As at tool Have in the E4 of the NII lower than E2 and E3 it can be seen that, the improvement of NII enters plateau.Additionally, glossiness is apparently higher than comparing Embodiment.C3 and E2 can compare, because they have roughly the same content of siloxane (Si%).Although the NII of E2 is more Low, but 20.Under glossiness strengthened.

E5-E8 uses PC-Si-1, and it provides bigger content of siloxane for same amount of PC-Si copolymer.Additionally, along with The amount of PC-Si-1 increases, and NII also increases.Additionally, glossiness is apparently higher than comparing embodiment.

Relatively C1-C4 and E1-E8, at poly-(aliphatic ester)-Copolycarbonate (PAE-BPA) and polysiloxanes-poly- There is synergy in the combination of carbonic ester (PC-Si), this provides the glossiness of improvement under 20 °.For all of enforcement Example, > the good shield effectiveness of 40dB is also kept.

Embodiment E10-E17

12 comparing embodiments C10-C21 and eight embodiments E10-E17 are described in the table 5A-5D.They use carbon Fiber, and be changed in terms of carbon fiber content, PC-Si type and PC-Si content.

Table 5A

Composition	Unit	C10	C11	C12	C13	C14	C15	C16	C17
										PAEBPALow	%		47.901
PAEBPAHigh	%		31.934
										PCLow	%	47.901		38.901	26.901	17.901	8.901	44.901	41.901
PCHigh	%	31.934		25.934	17.934	11.934	5.934	29.934	27.934
										PC-Si-1	%							5	10
PC-Si-2	%			15	35	50	65
										ADR 4368	%	0.085	0.085	0.085	0.085	0.085	0.085	0.085	0.085
Phosphite	%	0.08	0.08	0.08	0.08	0.08	0.08	0.08	0.08
										Carbon fiber	%	20	20	20	20	20	20	20	20
Si%	%	0	0	0.9	2.1	3	3.9	1	2
										PAEBPALow/PAEBPAHigh		1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Bending modulus	MPa	12153	11818	11773	10395	9171	7978	12390	12152
										Bending strength	MPa	239	239	236	202	175	144	242	242
NII,ISO	kJ/m2	10.6	11.8	14.3	15.6	15.9	15.3	12.5	13.5
										UNI,ISO	kJ/m2	45	42	45	36	36	34	42	45
NII,ASTM	J/m	118	125	158	161	156	146	139	158
										MAI,23℃	J	10.6	11.4	14.5	16.8	15.0	14.5	11.9	13.6
MAI,-20℃	J	8.5	9.9	12.3	13.3	12.8	12.4	10.1	11.0
										Chord modulus	MPa	14669	14510	14529	14142	14006	13842	15319	14570
Fracture strength	MPa	173	166	170	157	150	138	174	169
										Breaking strain	%	2.6	2.6	2.6	2.7	2.5	2.0	2.2	2.4

HDT	℃	140	126	139	138	136	134	140	140
										Glossiness, 20 °		2.9	11.62	5.2	6.3	6.2	8.2	6.8	7.4
Glossiness, 60 °		12.5	34.9	23.3	25.7	26.5	31.4	24.6	26.7

Table 5B

Composition	Unit	C18	C19	C20	C21	E10	E11	E12
									PAEBPALow					47.901	38.901	26.901	17.901
PAEBPAHigh					31.934	25.934	17.934	11.934
									PCLow		38.901	35.901	47.901
PCHigh		25.934	23.934	31.934
									PC-Si-1		15	20
PC-Si-2						15	35	50
									ADR 4368		0.085	0.085	0.085	0.085	0.085	0.085	0.085
Phosphite		0.08	0.08	0.08	0.08	0.08	0.08	0.08
									Carbon fiber		20	20	20	20	20	20	20
Si%		3	4	0	0	0.9	2.1	3
									PAEBPALow/PAEBPAHigh		1.5	1.5	1.5	1.5	1.5	1.5	1.5
Bending modulus	MPa	12059	11734	12121	12008	11725	10965	9026
									Bending strength	MPa	236	224	245	233	229	203	172
NII,ISO	kJ/m2	15.4	15.4	8.0	8.9	11.0	11.9	12.4
									UNI,ISO	kJ/m2	44	42	49	47	48	40	39
NII,ASTM	J/m	164	163
									MAI,23℃	J	15.6	16.8	11.2	11.5	14.4	16.2	15.6
MAI,-20℃	J	11.9	13.0	8.0	10.0	12.0	13.7	13.2
									Chord modulus	MPa	14460	14212	14992	14770	14623	14570	14353
Fracture strength	MPa	168	166	175	166	162	158	150
									Breaking strain	%	2.7	2.9	2.5	2.7	2.5	2.7	2.5
HDT	℃	133	133	138	124	126	126	126
									Glossiness, 20 °		7	7.4	3.9	24.6	13.4	26.8	11.1
Glossiness, 60 °		29.4	29.7	19.6	55.4	37.9	56.1	37.8

Table 5C

Composition	Unit	E13	E14	E15	E16	E17
							PAEBPALow	%	8.901	44.901	41.901	38.901	35.901
PAEBPAHigh	%	5.934	29.934	27.934	25.934	23.934
							PCLow	%
PCHigh	%
							PC-Si-1	%		5	10	15	20
PC-Si-2	%	65
							ADR 4368	%	0.085	0.085	0.085	0.085	0.085
Phosphite	%	0.08	0.08	0.08	0.08	0.08
							Carbon fiber	%	20	20	20	20	20
Si%	%	3.9	1	2	3	4
							PAEBPALow/PAEBPAHigh		1.5	1.5	1.5	1.5	1.5
Bending modulus	MPa	8502	11969	11501	11690	11365
							Bending strength	MPa	156	231	223	227	220
NII,ISO	kJ/m2	11.2	9.6	10.1		11.0
							UNI,ISO	kJ/m2	37	45	46	47	45
NII,ASTM	J/m
							MAI,23℃	J	15.1	13.6	14.9	14.5	15.0
MAI,-20℃	J	12.6	10.8	11.4	11.5	12.1

Chord modulus	MPa	14246	15038	14160	14473	14282
							Fracture strength	MPa	138	165	157	161	161
Breaking strain	%	1.9	2.1	2.4	2.5	2.7
							HDT	℃	129	125	125	126	126
Glossiness, 20 °		7.3	11.2	10.6	17.9	18.1
							Glossiness, 60 °		28.8	33.2	34.9	41.8	43.8

Seeing C10 and C11, use PAEBPA to replace Merlon, NII and MAI is roughly the same.But, PAEBPA has Higher glossiness and relatively low HDT.

Checking the C12-C19 compared with C10, along with the amount of PC-Si increases, NII and MAI adds 30-50%.Typically Ground, bending modulus declines, and HDT slightly reduces, and glossiness is increased slightly.Except glossiness, this also occurs in E10-E17 In.Relatively C12-15 and C16-C19, uses different PC-Si, and characteristic is roughly equal.

Comparison sheet 5A and 5B, when using PAEBPA to replace PC, NII is relatively low, and MAI is roughly equal, and HDT reduces, and light Pool degree is significantly higher.

Relatively E10-E13 and E14-E17, PC-Si-1 has slightly greater glossiness.Along with the level of PC-Si improves, NII keeps level substantially, and MAI is increased slightly, and HDT keeps level substantially.For E10-E13, glossiness is along with increase The content of PC-Si and reduce, and for E14-E17, glossiness increases along with the content of the PC-Si increased.For PC-Si-1 With PC-Si-2, it is apparent in the 2wt% of content of siloxane in overall composition relative to the Optimal Load of toughness NII and MAI And between 3wt%.

The disclosure is described with reference to illustrative embodiments.Obviously, once read and understand aforementioned in detail Describing, other people can modify and change.Desirably the disclosure should be interpreted that and comprises all such modifications and changes, As long as they are within the scope of claims or its equivalent.

Claims (60)

1. a composition, comprises:

First poly-(aliphatic ester)-Copolycarbonate, has from 15, the weight average molecular weight of 000Da to 40,000Da；

Polysiloxane-polycarbonate copolymer；And

The electromagnetic shielding agent of at least 3wt%, wherein said electromagnetic shielding agent comprises in metallic fiber and metal-coated fiber extremely Few one；

Wherein said composition shows

Notched Chalpy impact intensity according at least 110J/m that ASTM D256 measures；And

The glossiness of at least 90 measured at 20 ° according to ASTM D2457.

Composition the most according to claim 1, comprises the described electromagnetic shielding agent from 5wt% to 20wt%.

Composition the most according to claim 1, wherein said electromagnetic shielding agent is metallic fiber.

Composition the most according to claim 3, wherein said metallic fiber is stainless steel fibre.

Composition the most according to claim 1, wherein said composition shows the shield effectiveness of at least 30 decibels.

Composition the most according to claim 1, wherein said aliphatic ester adds up to 8 to 12 carbon atoms derived from having Aliphatic dicarboxylic acid.

Composition the most according to claim 1, the ester weight of wherein said first poly-(aliphatic ester)-Copolycarbonate Multiple unit is derived from decanedioic acid.

Composition the most according to claim 1, comprises described first poly-(the aliphatic ester)-poly-carbon of at maximum up to 85wt% Acid ester copolymer.

Composition the most according to claim 1, wherein said first poly-(aliphatic ester)-Copolycarbonate contain from The aliphatic ester unit of 2mol% to 13mol%.

10., according to the composition described in claim 9, wherein said first poly-(aliphatic ester)-Copolycarbonate contains There is the carbonate unit derivative from bisphenol-A of 87mol% to 98mol%.

11. compositions according to claim 9, wherein said aliphatic ester unit is derived from decanedioic acid.

12. compositions according to claim 1, comprise second poly-(aliphatic ester)-Copolycarbonate further；Its Described in the weight average molecular weight of second poly-(aliphatic ester)-Copolycarbonate more than described first poly-(aliphatic ester)-poly- The weight average molecular weight of carbonate copolymer.

13. compositions according to claim 12, wherein said first poly-(aliphatic ester)-Copolycarbonate and institute State the weight ratio of second poly-(aliphatic ester)-Copolycarbonate for from 1:4 to 5:2.

14. compositions according to claim 12, wherein said first poly-(aliphatic ester)-Copolycarbonate has From 15, the weight average molecular weight of 000Da to 25,000Da, and described second poly-(aliphatic ester)-Copolycarbonate has From the weight average molecular weight of 30,000Da to 40,000Da.

15. compositions according to claim 12, comprise from described first poly-(aliphatic ester) of 10wt% to 55wt%- Copolycarbonate.

16. compositions according to claim 12, comprise from described second poly-(aliphatic ester) of 5wt% to 40wt%- Copolycarbonate.

17. compositions according to claim 1, comprise the described polysiloxane-polycarbonate of at maximum up to 70wt% altogether Polymers.

18. compositions according to claim 1, the siloxane blocks of wherein said polysiloxane-polycarbonate copolymer Chain length is from 30 to 100.

19. compositions according to claim 1, the siloxane blocks of wherein said polysiloxane-polycarbonate copolymer Chain length is from 35 to 55.

20. compositions according to claim 1, wherein said polysiloxane-polycarbonate copolymer has from 15wt% Siloxane blocks content to 25wt%.

21. compositions according to claim 1, wherein said composition has from the siloxanes of 0.5wt% to 5wt% embedding Duan Hanliang.

22. compositions according to claim 1, wherein said composition has the siloxanes from 0.9wt% to 4.0wt% Block concentration.

23. compositions according to claim 1, wherein said composition has the siloxanes from 2.0wt% to 3.0wt% Block concentration.

24. compositions according to claim 1, wherein said composition comprises from being derived from of 0.5wt% to 6wt% described The siloxanes of polysiloxane-polycarbonate copolymer.

25. compositions according to claim 1, wherein said composition has the total soft block contents less than 3.5wt%.

26. compositions according to claim 1, wherein said composition shows to be measured at least according to ISO 178 The bending modulus of 2000Mpa.

27. compositions according to claim 1, wherein said composition shows to be measured at least according to ASTM D 256 The notched Chalpy impact intensity of 130J/m.

28. compositions according to claim 1, wherein said composition show at least 92 the glossiness of 20 °.

29. compositions according to claim 1, wherein said composition shows

Notched Chalpy impact intensity according at least 140J/m that ASTM D 256 measures；

The glossiness of at least 92 measured at 20 ° according to ASTM D 2457；And

According to the shield effectiveness of at least 30 decibels that ASTM D4935 measures.

30. compositions according to claim 1, wherein said composition shows according to ASTM D 2457 60 ° of measurements At least 98 glossiness.

31. 1 kinds by the goods made according to the composition in any of the one of claim 1-30.

32. goods according to claim 31, have and have at least 0.3mm and the wall less than 0.8mm thickness,

Wherein said composition shows

Notched Chalpy impact intensity according at least 110J/m that ASTM D256 measures；And

The glossiness of at least 90 measured at 20 ° according to ASTM D2457.

33. goods according to claim 32, wherein said goods are mobile phone, MP3 player, computer, notes This computer, camera, video recorder, electronic plane computer, pager, hand telephone, video game machine, calculator, nothing Line automobile input unit, automobile component, filter housings, luggage truck, office chair, kitchen appliance, electric housing, electric connector, A part for lighting, light emitting diode, electric component or telecommunications components.

34. compositions according to claim 1, comprise:

First poly-(aliphatic ester)-Copolycarbonate, has from 15, the weight average molecular weight of 000Da to 25,000Da；

Second poly-(aliphatic ester)-Copolycarbonate, has from 30, the weight average molecular weight of 000Da to 40,000Da；

Described polysiloxane-polycarbonate copolymer；And

Metallic fiber；

Wherein said composition shows

Notched Chalpy impact intensity according at least 110J/m that ASTM D256 measures；And

The glossiness of at least 90 measured at 20 ° according to ASTM D2457.

35. 1 kinds of compositions, comprise:

First poly-(aliphatic ester)-Copolycarbonate, has from 15, the weight average molecular weight of 000Da to 40,000Da；

Polysiloxane-polycarbonate copolymer；And

The carbon fiber of 5 to 20wt%；

Wherein said composition shows

According to ISO 180 at 23 DEG C, at least 9.5kJ/m that 3mm measures²Notched Chalpy impact intensity；And

According to ASTM D3763 at 23 DEG C of multi-axial impact strength MAI of at least 13J measured.

36. compositions according to claim 35, wherein said aliphatic ester is amounted to the fat of 8 to 12 carbon atoms by having Fat race dicarboxylic acids derives.

37. compositions according to claim 35, the ester of wherein said first poly-(aliphatic ester)-Copolycarbonate Repetitive is derived from decanedioic acid.

38. compositions according to claim 35, described first poly-(aliphatic ester) comprising at maximum up to 85wt%-gather Carbonate copolymer.

39. compositions according to claim 35, wherein said first poly-(aliphatic ester)-Copolycarbonate contains From the aliphatic ester unit of 2mol% to 13mol%.

40. contain according to the composition described in claim 39, wherein said first poly-(aliphatic ester)-Copolycarbonate The carbonate unit derived from bisphenol-A of 87mol% to 98mol%.

41. according to the composition described in claim 39, and wherein said aliphatic ester unit is derived from decanedioic acid.

42. compositions according to claim 35, comprise second poly-(aliphatic ester)-Copolycarbonate further, The weight average molecular weight of wherein said second poly-(aliphatic ester)-Copolycarbonate more than described first poly-(aliphatic ester)- The weight average molecular weight of Copolycarbonate.

43. compositions according to claim 42, wherein said first poly-(aliphatic ester)-Copolycarbonate and institute State the weight ratio of second poly-(aliphatic ester)-Copolycarbonate for from 1:4 to 5:2.

44. compositions according to claim 42, wherein said first poly-(aliphatic ester)-Copolycarbonate has From 15, the weight average molecular weight of 000Da to 25,000Da, and described second poly-(aliphatic ester)-Copolycarbonate has From the weight average molecular weight of 30,000Da to 40,000Da.

45. compositions according to claim 42, comprise from described first poly-(aliphatic ester) of 5wt% to 50wt%- Copolycarbonate.

46. compositions according to claim 42, comprise from described second poly-(aliphatic ester) of 5wt% to 30wt%- Copolycarbonate.

47. compositions according to claim 35, comprise the described polysiloxane-polycarbonate of at maximum up to 70wt% altogether Polymers.

48. compositions according to claim 35, the siloxane blocks of wherein said polysiloxane-polycarbonate copolymer Chain length is from 30 to 100.

49. compositions according to claim 35, the siloxane blocks of wherein said polysiloxane-polycarbonate copolymer Chain length is from 35 to 55.

50. compositions according to claim 35, wherein said polysiloxane-polycarbonate copolymer has from 15wt% Siloxane blocks content to 25wt%.

51. compositions according to claim 35, wherein said composition has the siloxanes from 0.5wt% to 5wt% Block concentration.

52. compositions according to claim 35, wherein said composition has the silica from 0.9wt% to 4.0wt% Alkane block concentration.

53. compositions according to claim 35, wherein said composition has the silica from 2.0wt% to 3.0wt% Alkane block concentration.

54. compositions according to claim 35, it is described that wherein said composition comprises being derived from of 0.5wt% to 6wt% The siloxanes of polysiloxane-polycarbonate copolymer.

55. compositions according to claim 35, wherein said composition shows

According to ISO 180 at 23 DEG C, at least 11kJ/m that 3mm measures²Notched Chalpy impact intensity；And

According to ASTM D3763 at 23 DEG C of multi-axial impact strength MAI of at least 14J measured.

56. compositions according to claim 35, wherein said composition show at least 9000Mpa bending modulus and The glossiness of at least 10 measured at 20 ° according to ASTM D 2457.

57. compositions according to claim 35, wherein said composition shows at least 10, the bending modulus of 000Mpa Glossiness with at least 15 measured at 20 ° according to ASTM D 2457.

58. 1 kinds by the goods made according to the composition according to any one of claim 35 to 57.

59. goods according to claim 58, wherein said goods have and have at least 0.3mm and thick less than 0.8mm The wall of degree.

60. goods according to claim 58, wherein said goods are mobile phone, MP3 player, computer, notes This computer, camera, video recorder, electronic plane computer, pager, hand telephone, video game machine, calculator, nothing Line automobile input unit, automobile component, filter housings, luggage truck, office chair, kitchen appliance, electric housing, electric connector, A part for lighting, light emitting diode, electric component or telecommunications components.